Method and structure for thin film photovoltaic cell using similar material junction

ABSTRACT

A method for forming a thin film photovoltaic device. The method provides a transparent substrate including a surface region. A first electrode layer overlies the surface region. A copper layer is formed overlying the first electrode layer and an indium layer is formed overlying the copper layer to form a multi-layered structure. At least the multi-layered structure is subjected to a thermal treatment process in an environment containing a sulfur bearing species to forming a bulk copper indium disulfide. The bulk copper indium disulfide material has a surface region characterized by a copper poor surface region having a copper to indium atomic ratio of less than about 0.95:1 and n-type impurity characteristics. The bulk copper indium disulfide material excluding the copper poor surface region forms an absorber region and the copper poor surface region forms at least a portion of a window region for the thin film photovoltaic device. The method optionally forms a high resistivity transparent material having an intrinsic semiconductor characteristic overlying the copper poor surface region. A second electrode layer overlies the high resistivity transparent layer.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent Application No. 61/116,625, filed Nov. 20, 2008, entitled “METHOD AND STRUCTURE FOR THIN FILM PHOTOVOLTAIC CELL USING SIMILAR MATERIAL JUNCTION” by inventor Howard W. H. Lee, commonly assigned and incorporated by reference herein for all purposes.

BACKGROUND OF THE INVENTION

The present invention relates generally to photovoltaic materials and manufacturing method. More particularly, the present invention provides a method and structure for manufacture of thin film photovoltaic cells. Merely by way of example, the present method and materials include absorber materials made of copper indium disulfide species, copper tin sulfide, iron disulfide, or others for single junction cells or multi junction cells.

From the beginning of time, mankind has been challenged to find way of harnessing energy. Energy comes in the forms such as petrochemical, hydroelectric, nuclear, wind, biomass, solar, and more primitive forms such as wood and coal. Over the past century, modern civilization has relied upon petrochemical energy as an important energy source. Petrochemical energy includes gas and oil. Gas includes lighter forms such as butane and propane, commonly used to heat homes and serve as fuel for cooking Gas also includes gasoline, diesel, and jet fuel, commonly used for transportation purposes. Heavier forms of petrochemicals can also be used to heat homes in some places. Unfortunately, the supply of petrochemical fuel is limited and essentially fixed based upon the amount available on the planet Earth. Additionally, as more people use petroleum products in growing amounts, it is rapidly becoming a scarce resource, which will eventually become depleted over time.

More recently, environmentally clean and renewable sources of energy have been desired. An example of a clean source of energy is hydroelectric power. Hydroelectric power is derived from electric generators driven by the flow of water produced by dams such as the Hoover Dam in Nevada. The electric power generated is used to power a large portion of the city of Los Angeles in California. Clean and renewable sources of energy also include wind, waves, biomass, and the like. That is, windmills convert wind energy into more useful forms of energy such as electricity. Still other types of clean energy include solar energy. Specific details of solar energy can be found throughout the present background and more particularly below.

Solar energy technology generally converts electromagnetic radiation from the sun to other useful forms of energy. These other forms of energy include thermal energy and electrical power. For electrical power applications, solar cells are often used. Although solar energy is environmentally clean and has been successful to a point, many limitations remain to be resolved before it becomes widely used throughout the world. As an example, one type of solar cell uses crystalline materials, which are derived from semiconductor material ingots. These crystalline materials can be used to fabricate optoelectronic devices that include photovoltaic and photodiode devices that convert electromagnetic radiation into electrical power. However, crystalline materials are often costly and difficult to make on a large scale. Additionally, devices made from such crystalline materials often have low energy conversion efficiencies. Other types of solar cells use “thin film” technology to form a thin film of photosensitive material to be used to convert electromagnetic radiation into electrical power. Similar limitations exist with the use of thin film technology in making solar cells. That is, efficiencies are often poor. Additionally, film reliability is often poor and cannot be used for extensive periods of time in conventional environmental applications. Often, thin films are difficult to mechanically integrate with each other. These and other limitations of these conventional technologies can be found throughout the present specification and more particularly below.

From the above, it is seen that improved techniques for manufacturing photovoltaic materials and resulting devices are desired.

BRIEF SUMMARY OF THE INVENTION

According to embodiments of the present invention, a method and a structure for forming thin film semiconductor materials for photovoltaic applications are provided. More particularly, the present invention provides a method and structure for forming thin film semiconductor materials used for manufacturing photovoltaic cells. Merely by way of example, the present method and materials include absorber materials made of copper indium disulfide species, copper tin sulfide, iron disulfide, or others for single junction cells or multi junction cells.

In a specific embodiment, a method for forming a thin film photovoltaic device is provided. The method includes providing a transparent substrate including a surface region. A first electrode layer is formed overlying the surface region. The method includes forming a copper layer overlying the first electrode layer and forming an indium layer overlying the copper layer to form a multi-layered structure. In a specific embodiment, the method includes subjecting at least the multi-layered structure to a thermal treatment process in an environment containing sulfur bearing species and forming a bulk copper indium disulfide material from at least the treatment process of the multi-layered structure. In a specific embodiment, the method forms a bulk copper indium disulfide material from at least the treatment process of the multi-layered structure. The bulk copper indium disulfide material having a surface region characterized by a copper poor surface region comprising a copper to indium atomic ratio of less than about 0.95:1. In a specific embodiment, the copper poor surface region has n-type impurity characteristics. In a specific embodiment, the bulk copper indium disulfide material excluding the copper poor surface region forms an absorber region and the copper poor surface region forming at least a portion of a window region for the photovoltaic cell. In a specific embodiment, the method includes forming a high resistivity transparent material overlying the copper poor surface region having the n-type impurity characteristics. The high resistivity transparent layer uses a semiconductor material having an intrinsic semiconductor characteristic in a specific embodiment. A second electrode layer is formed overlying the high resistivity transparent layer.

In an alternative embodiment, a thin film photovoltaic device is provided. The thin film photovoltaic device includes a substrate comprising a surface region. The thin film photovoltaic device includes a first electrode layer overlying the surface region. A chalcopyrite material including a chalcopyrite material surface region overlies the first electrode layer. In a specific embodiment, the chalcopyrite material includes a copper indium disulfide material and a copper poor copper indium disulfide surface region. The copper poor copper indium disulfide surface region has an atomic ratio of Cu:In of about 0.99 and less and has an n type impurity characteristics. In a specific embodiment, the copper poor copper indium disulfide surface region provides for a window layer for the photovoltaic device. The thin film photovoltaic device also includes a second electrode layer overlying the window layer.

In a yet alternative embodiment, a thin film photovoltaic device is provided. The thin film photovoltaic device includes a substrate including a surface region. A first electrode layer overlies the surface region. The thin film photovoltaic device includes an absorber region overlying the first electrode layer. In a specific embodiment, the absorber region includes a bulk copper indium disulfide material. The thin film photovoltaic device includes a window region comprising a surface region of the bulk copper indium disulfide material. The surface region of the bulk copper indium disulfide material is characterized by a copper poor surface region having a copper to indium atomic ratio of less than about 0.95:1. In a specific embodiment, the copper poor surface region having n-type impurity characteristics. The thin film photovoltaic device may include a high resistivity transparent material overlying the copper poor surface region having the n-type impurity characteristics. The high resistivity transparent layer includes a semiconductor material having an intrinsic semiconductor characteristic. The thin film photovoltaic device includes a second electrode layer overlying the high resistivity transparent layer. The second electrode layer includes a zinc oxide material having p-type impurity characteristics in a specific embodiment.

Many benefits are achieved by ways of present invention. For example, the present invention uses starting materials that are commercially available to form a thin film of semiconductor bearing material overlying a suitable substrate member. The thin film of semiconductor bearing material can be further processed to form a semiconductor thin film material of desired characteristics, such as atomic stoichiometry, impurity concentration, carrier concentration, doping, and others. In a specific embodiment, the thin film semiconductor material can be provided using a copper indium disulfide material. In a specific embodiment, the copper indium disulfide material is characterized by a bandgap of about 1.55 eV. Additionally, embodiments according to the present invention use environmentally friendly materials that are relatively less toxic than other thin-film photovoltaic materials. In a preferred embodiment, the present method and resulting structure is substantially free from a parasitic junction on an absorber layer based upon a copper poor chalcopyrite material. In a specific embodiment, the present method uses the copper poor chalcopyrite material, which has an n type impurity characteristics, as a window layer for the photovoltaic cell. Also in a preferred embodiment, the open circuit voltage of the chalcopyrite material such as copper indium disulfide ranges from about 0.8 volts and greater and preferably 0.9 volts and greater or 1.0 volts and greater up to 1.2 volts. Depending on the embodiment, one or more of the benefits can be achieved. These and other benefits will be described in more detailed throughout the present specification and particularly below.

Merely by way of example, the present method and materials include absorber materials made of copper indium disulfide species, copper tin sulfide, iron disulfide, or others for single junction cells or multi junction cells.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1-8 are schematic diagrams illustrating a method and structure for forming a thin film photovoltaic device according to an embodiment of the present invention;

FIGS. 9-10 are simplified diagrams illustrating a method and structure for forming a thin film photovoltaic device including a copper poor surface region for a window layer according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

According to embodiments of the present invention, a method and a structure for forming semiconductor materials for photovoltaic applications are provided. More particularly, the present invention provides a method for manufacturing thin film photovoltaic devices. Merely by way of example, the method has been used to provide a copper indium disulfide thin film material for high efficiency solar cell application. But it would be recognized that the present invention has a much broader range of applicability, for example, embodiments of the present invention may be used to form other semiconducting thin films or multi layers comprising iron sulfide, cadmium sulfide, zinc selenide, and others, and metal oxides such as zinc oxide, iron oxide, copper oxide, and others.

FIG. 1 is a schematic diagram illustrating a process of a method for forming a thin film photovoltaic device according to an embodiment of the present invention. The diagram is merely an example, which should not unduly limit the claims herein. One skilled in the art would recognize other variations, modifications, and alternatives. As shown in FIG. 1, a substrate 110 is provided. In an embodiment, the substrate 110 includes a surface region 112 and is held in a process stage within a process chamber (not shown). In another embodiment, the substrate 110 is an optically transparent solid material. For example, the substrate 110 can be a glass, quartz, fused silica, or a plastic, or metal, or foil, or semiconductor, or other composite materials. Depending upon the embodiment, the substrate can be a single material, multiple materials, which are layered, composites, or stacked, including combinations of these, and the like. Of course there can be other variations, modifications, and alternatives.

FIG. 2 is a schematic diagram illustrating a process of the method for forming a thin film photovoltaic device according to an embodiment of the present invention. The diagram is merely an example, which should not unduly limit the claims herein. One skilled in the art would recognize other variations, modifications, and alternatives. As shown in FIG. 2, the present invention provides a process for forming a thin film photovoltaic device is to form an electrode layer. In particular, a first electrode layer 120 is formed overlying the surface region 112 of the substrate 110. For example, the first electrode layer 120 can be made of molybdenum using sputtering, evaporation (e.g., electron beam), electro plating, combination of these, and the like according to a specific embodiment. The thickness of the first electrode layer can be ranged from 100 nm to 2 micron and others, characterized by resistivity of about 100 Ohm/cm² to 10 Ohm/cm² and less according to a specific embodiment. In a preferred embodiment, the first electrode is made of molybdenum or tungsten, but can be others like copper, chromium, aluminum, nickel, or platinum. Of course, there can be other variations, modifications, and alternatives.

FIG. 3 is a schematic diagram illustrating a process of the method for forming a thin film photovoltaic device according to an embodiment of the present invention. The diagram is merely an example, which should not unduly limit the claims herein. One skilled in the art would recognize other variations, modifications, and alternatives. As shown is a process of forming a copper layer overlying the first electrode layer formed in last process. In particular, a copper (Cu) layer 130 is formed overlying the first electrode layer 120. For example, the copper layer is formed using a sputtering process. In one example, a DC magnetron sputtering process can be used to deposit Cu layer 130 onto the first electrode layer 120 under a following condition. The deposition pressure (using Ar gas) is controlled to be about 6.2 mTorr. The gas flow rate is set to about 32 sccm. The deposition temperature can be just at room temperature without need of intentionally heating the substrate. Of course, minor heating may be resulted due to the plasma generated during the deposition. Additionally, the DC power supply of about 115 W may be required. According to certain embodiments, DC power in a range from 100 W to 150 W is suitable depending specific cases with different materials. The full deposition time for a Cu layer of 330 nm thickness is about 6 minutes or more. Of course, the deposition condition can be varied and modified according to a specific embodiment.

In a preferred embodiment, the method includes forming a barrier layer 125 overlying the first electrode layer to form an interface region between the first electrode layer and the copper layer. In a specific embodiment, the interface region is maintained substantially free from metal disulfide layer having a semiconductor characteristic that is different from the copper indium disulfide material during later processing steps. Depending upon the embodiment, the barrier layer has suitable conductive characteristics and can be reflective to allow electromagnetic radiation to reflect back or can also be transparent or the like. In a specific embodiment, the barrier layer is selected from platinum, titanium, chromium, or silver. Of course, there can be other variations, modifications, and alternatives.

FIG. 4 is a schematic diagram illustrating a process of the method for forming a thin film photovoltaic device according to an embodiment of the present invention. The diagram is merely an example, which should not unduly limit the claims herein. One skilled in the art would recognize other variations, modifications, and alternatives. As shown, a process of providing an indium (In) layer overlying the copper layer is illustrated. In particular, the indium layer 140 is formed overlying the copper layer 130. For example, the indium layer is deposited over the copper layer using a sputtering process. In one example, a DC magnetron sputtering process can be used to deposit In layer 140 overlying the Cu layer 120 under a similar condition for depositing the Cu layer. The deposition time for the indium layer may be shorter than that for Cu layer. For example, 2 minutes and 45 seconds may be enough for depositing an In layer of about 410 nm in thickness according to a specific embodiment. In another example, the indium layer is provided overlying the copper layer by an electro plating process, or others dependent on specific embodiment.

According to embodiments of the present invention, FIGS. 1 through 4 illustrate a formation of a multilayered structure 150 comprising copper and indium on a transparent substrate provided by processes of a method of forming a thin film photovoltaic device. In one embodiment, the copper layer 130 as well as the indium layer 140 are provided with a selected stoichiometry to ensure that the multilayered structure 150 is a Cu-rich material with an atomic ratio of Cu:In greater than 1 therein. For example, the atomic ratio of Cu:In can be in a range from 1.2:1 to 2.0:1 or larger depending upon the specific embodiment. In an implementation, the atomic ratio of Cu:In is between 1.35:1 and 1.60:1. In another implementation, the atomic ratio of Cu:In is selected to be about 1.55:1. In a preferred embodiment, the Cu:In ratio is introduced as copper rich, which consumes substantially all of the indium species, in the resulting structure. In a specific embodiment, the formation process of indium layer 140 substantially causes no change in atomic stoichiometry in the copper layer 130 formed earlier. In another specific embodiment, the formation process of the indium layer 140 is performed earlier overlying the first electrode layer 120 while the formation process of the copper layer 130 is performed later overlying the indium layer 140.

FIG. 5 is a schematic diagram illustrating a process of the method for forming a thin film photovoltaic device according to an embodiment of the present invention. The diagram is merely an example, which should not unduly limit the claims herein. One skilled in the art would recognize other variations, modifications, and alternatives. As shown, the formed multilayered structure 150 comprising at least an indium layer 140 over a copper layer 130 is subjected to a thermal treatment process 200 in an environment containing a sulfur bearing species 210 at an adequate pressure and at a temperature of about 400 Degrees Celsius to about 600 Degrees Celsius for about three to fifteen minutes for a rapid thermal process according to a specific embodiment. In one example, the sulfur bearing species are in a fluid phase. As an example, the sulfur can be provided in a solution, which has dissolved Na₂S, CS₂, (NH₄)₂S, thiosulfate, and others. In another example, the sulfur bearing species 210 are hydrogen sulfide in gas phase. In other embodiments, the sulfur can be provided in a solid phase. In a solid phase, elemental sulfur can be heated and allowed to boil, which vaporizes into a gas phase, e.g., S_(n). In a specific embodiment, the gas phase sulfur is allowed to react to the indium/copper layers. In other embodiments, other combinations of sulfur species can be used. Of course, the thermal treatment process 200 includes certain predetermined ramp-up and ramp down period with certain predetermined speed for temperature changes. For example, the thermal treatment process is a rapid thermal annealing process. The hydrogen sulfide gas is provided through one or more entry valves with flow rate control into the process chamber where the hydrogen sulfide gas pressure is under controlled by one or more pumps. Of course, there can be other variations, modifications, and alternatives.

In a specific embodiment, the sulfur can be provided as a layer overlying the indium and copper layers or copper and indium layers. In a specific embodiment, the sulfur material is provided as a thin layer or patterned layer. Depending upon the embodiment, the sulfur can be provided as a slurry, powder, solid material, gas, paste, or other suitable form. Of course, there can be other variations, modifications, and alternatives.

Referring to the FIG. 5, the thermal treatment process 200 causes a reaction between copper indium material within the multilayered structure 150 and the sulfur bearing species 210, thereby forming a layer of copper indium disulfide material (or a copper indium disulfide thin film) 220. In one example, the copper indium disulfide material or copper indium disulfide thin film 220 is transformed by incorporating sulfur ions/atoms stripped or decomposed from the sulfur bearing species into the multilayered structure 150 with indium atoms and copper atoms mutually diffused therein. In an embodiment, the thermal treatment process 200 would result in a formation of a cap layer over the transformed copper indium disulfide material 220. The cap layer contains a thickness of substantially copper sulfide material 221 but substantially free of indium atoms. The copper sulfide material 221 includes a surface region 225 of the same copper sulfide material substantially free of indium atoms. In a specific embodiment, the formation of this cap layer is under Cu-rich conditions for the original Cu—In bearing multilayered structure 150. Depending on the applications, the thickness of the copper sulfide material 221 is on an order of about five to ten nanometers and greater based on original multilayered structure 150 with indium layer 140 overlying copper layer 130. Of course, there can be other variations, modifications, and alternatives.

FIG. 6 is a schematic diagram illustrating a process of the method for forming a thin film photovoltaic device according to an embodiment of the present invention. The diagram is merely an example, which should not unduly limit the claims herein. One skilled in the art would recognize other variations, modifications, and alternatives. As shown in FIG. 6, a dip process 300 is performed to the copper sulfide material 221 that covers the copper indium disulfide thin film 220. In particular, the dip process is performed by exposing the surface region 225 to 1 to about 10 weight % solution of potassium cyanide 310 according to a specific embodiment. The potassium cyanide acts as an etchant that is capable of selectively removing copper sulfide material 221. The etching process starts from the exposed surface region 225 and down to the thickness of the copper sulfide material 221 and substantially stopped at the interface between the copper sulfide material 221 and copper indium disulfide material 220. As a result the copper sulfide cap layer 221 is selectively removed by the etching process so that a new surface region 228 of the remaining copper indium disulfide thin film 220 is exposed according to a specific embodiment. In a preferred embodiment, the etch selectivity is about 1:100 or more between copper sulfide and copper indium disulfide. In other embodiments, other selective etching species can be used. In a specific embodiment, the etching species can be hydrogen peroxide. In other embodiments, other techniques including electro-chemical etching, plasma etching, sputter-etching, or any combination of these can be used. In a specific embodiment, the copper sulfide material can be mechanically removed, chemically removed, electrically removed, or any combination of these, among others. In a specific embodiment, the absorber layer made of copper indium disulfide is about 1 to 10 microns, but can be others. Of course, there can be other variations, modifications, and alternatives.

FIG. 7 is a schematic diagram illustrating a process of the method for forming a thin film photovoltaic device according to an embodiment of the present invention. The diagram is merely an example, which should not unduly limit the claims herein. One skilled in the art would recognize other variations, modifications, and alternatives. As shown in FIG. 7, a p-type copper indium disulfide film 320 is formed. In certain embodiments, the previously-formed copper indium disulfide material 220 has possessed a p-type semiconducting characteristic and is substantially the same as the p-type copper indium disulfide film 320. In another embodiment, the copper indium disulfide material 220 is subjected to additional doping process to provide a p-type impurity density therein for the purpose of an optimum I-V characteristic of the high efficiency thin film photovoltaic devices. In a specific embodiment, aluminum species are mixed into the copper indium disulfide material 220. In another example, the copper indium disulfide material 220 is mixed with a copper indium aluminum disulfide material to form the film 320. Of course, there can be other variations, modifications, and alternatives.

Subsequently, a window layer 310 is formed overlying the p-type copper indium disulfide material 320. The window layer 310 can be selected from a group materials consisting of a cadmium sulfide (CdS), a zinc sulfide (ZnS), zinc selenium (ZnSe), zinc oxide (ZnO), zinc magnesium oxide (ZnMgO), or others and may be doped with impurities for conductivity, e.g., n⁺-type. The window layer 310 is intended to serve another part of a PN junction associated with a photovoltaic cell. Therefore, the window layer 310, during or after its formation, is heavily doped to form an n⁺-type semiconductor layer. In one example, indium species are used as the doping material to cause formation of the n⁺-type characteristic associated with the window layer 310. In another example, the doping process is performed using suitable conditions. In a specific embodiment, ZnO window layer that is doped with aluminum can range from about 200 to 500 nanometers. Of course, there can be other variations, modifications, and alternative

FIG. 8 is a schematic diagram illustrating a process of the method for forming a thin film photovoltaic device according to an embodiment of the present invention. The diagram is merely an example, which should not unduly limit the claims herein. One skilled in the art would recognize other variations, modifications, and alternatives. As shown in FIG. 8, a conductive layer 330 is provided at least on a selected portion of window layer 310 to form a top electrode layer for the photovoltaic device. In one embodiment, conductive layer 330 is a transparent conductive oxide (TCO) layer. For example, TCO can be selected from a group consisting of In₂O₃:Sn (ITO), ZnO:Al (AZO), SnO₂:F (TFO), or others. In another embodiment, the formation of the TCO layer is followed by a patterning step for effectively carried out the function of top electrode layer for the photovoltaic device with considerations of maximizing the efficiency of the thin film based photovoltaic devices. In certain embodiments, the TCO layer can function as a window layer, which essentially eliminates a separate window layer. Of course there can be other variations, modifications, and alternatives.

In a preferred embodiment, the present method maintains an interface region between the first electrode layer overlying the surface region and the copper indium disulfide material substantially free from a metal disulfide layer having different semiconductor characteristics from the copper indium disulfide material. Depending upon the type of first electrode material, the metal disulfide layer is selected from molybdenum disulfide layer or the like. In a specific embodiment, the interface region is characterized by a surface morphology substantially preventing any formation of the metal disulfide layer, which is characterized by a thickness of about 5 to 10 nanometers. In a preferred embodiment, the present method includes a thermal process during at least the maintaining process or a portion of the maintaining process of at least 300 Degrees Celsius and greater to prevent any formation of the metal disulfide layer, which can be the molybdenum disulfide or like layer. Of course, there can be other variations, modifications, and alternatives.

In a specific embodiment, the present invention provides a method for forming a thin film photovoltaic device, which is outlined below.

-   -   1. Start;     -   2. Provide a transparent substrate comprising a surface region;     -   3. Form a first electrode layer overlying the surface region;     -   4. Form a copper layer overlying the first electrode layer;     -   5. Form an indium layer overlying the copper layer to form a         multi-layered structure (alternatively indium is formed first or         a multiple layers are sandwiched together);     -   6. Subject at least the multi-layered structure to a thermal         treatment process in an environment containing a sulfur bearing         species;     -   7. Form a bulk copper indium disulfide material from at least         the treatment process of the multi-layered structure, the copper         indium disulfide material comprising a copper-to-indium atomic         ratio ranging from about 1.2:1 to about 2:1 or 1.35:1 to about         1.60:1 (or preferably and alternatively from about 0.99:1 ; or         0.95:1 and less) and a thickness of substantially copper sulfide         material having a copper sulfide surface region;     -   8. Remove the thickness of the copper sulfide material to expose         a surface region having a copper poor surface region comprising         a copper to indium atomic ratio of less than about 0.95:1 or         0.99:1, the copper poor surface region has a n type impurity         characteristics; and     -   9. Form an optional high resistivity transparent layer overlying         the copper poor surface region having the n type impurity         characteristic;     -   10. Form a second electrode layer; and     -   11. Perform other steps, as desired.

The above sequence of steps provides a method according to an embodiment of the present invention. In a specific embodiment, the present invention provides a method and resulting photovoltaic structure using a copper poor surface region for the window layer and free from parasitic junction regions in the absorber layer. Other alternatives can also be provided where steps are added, one or more steps are removed, or one or more steps are provided in a different sequence without departing from the scope of the claims herein. Details of the present method and structure can be found throughout the present specification and more particularly below.

FIGS. 9-11 are simplified diagrams illustrating a method and structure for forming a thin film photovoltaic device according to an embodiment of the present invention. These diagrams are merely examples, which should not unduly limit the scope of the claims herein. One of ordinary skill in the art would recognize other variations, modifications, and alternatives. In a specific embodiment, the present method begins with partially completed photovoltaic device 900. As shown, the device includes a transparent substrate 901 comprising a surface region, although other substrates can be used. The photovoltaic device also includes a first electrode layer 903 overlying the surface region. In a specific embodiment, the first electrode layer can be any conductive material including conductive metals, oxides, and semiconductor or combinations of these, as well as any material described herein and outside of the present specification.

In a specific embodiment, the photovoltaic device includes a chalcopyrite material, which acts as an absorber 905 for the photovoltaic device. As shown, the chalcopyrite material can include, among others, copper indium disulfide material, copper indium aluminum disulfide, copper indium gallium disulfide, combinations of these, and others. In a specific embodiment, the chalcopyrite material is copper rich, or alternatively copper poor and characterized by one or more portions having a copper to indium atomic ratio of 0.99:1 and less or 0.95:1 and less. In a preferred embodiment, the copper indium disulfide material has one or more copper poor regions, which are preferably compensated using an ionic species. Of course, there can be other variations, modifications, and alternatives. In a specific embodiment, the chalcopyrite has a thin layer of copper sulfide 907, which has been previously described, as may remain as a residue or fixed material when the bulk material is copper rich. Of course, there can be other variations, modifications, and alternatives.

Referring to FIG. 10, the method selectively removes the thin layer of copper sulfide. In a specific embodiment, the thin layer is removed 909 using a solution of potassium cyanide (KCN) or other suitable technique, e.g., dry etching, plasma etching, sputtering, or others. In a specific embodiment, the method may cause formation of a copper poor surface region 1001. In a specific embodiment, the copper poor surface is characterized by a copper to indium atomic ratio of less than about 0.95:1 or 0.99:1. In a specific embodiment, the copper poor surface region is characterized as an n-type chalcopyrite material, which forms a PN junction with the p-type copper indium disulfide material, which can be rich in copper. The copper poor surface region can function as a window layer for the photovoltaic device in a specific embodiment. In certain embodiments, the copper poor surface region may be further treated to provide for an adequate n-type impurity concentration for proper and efficient charge separation for the photovoltaic cell. Of course, there can be other variations, modifications, and alternatives.

Depending on the embodiment, the copper poor surface region may have defects such as one or more pin holes in a thickness of the copper poor surface region. In a specific embodiment, the method includes forming an optional high resistivity transparent (HRT) layer 1003 overlying the copper poor surface region, which has n-type impurity characteristics. The HRT layer can use an intrinsic semiconductor material that forms a second transparent conductive oxide 1005 in a specific embodiment. For example, for an aluminum doped zinc oxide material as the second transparent conductive oxide, the HRT layer can use an intrinsic zinc oxide material. In an alternative embodiment, the HRT layer may be an intrinsic semiconductor material that forms a window layer for the photovoltaic cell. For example, for a CIGS based photovoltaic device using an n-type cadmium sulfide material as a window, the HRT layer may use an intrinsic cadmium sulfide material, but can be other materials. Of course one skilled in the art would recognize other variations, modifications, and alternatives. In an implementation of the present invention, the HRT layer used intrinsic zinc oxide material or intrinsic tin oxide material having a doping level between about 1×10¹¹ and about 1×10¹³ cm⁻³. The HRT layer can have a thickness between about 100 nm and 1000 nm and a resistance between 1 ohm/square and 0.0001 ohm/square. As merely an example, the second transparent conductive oxide material and the corresponding HRT layer can include tin doped indium oxide, indium oxide, fluorine doped tin oxide, tin oxide, AZO, and others. In a specific embodiment, the highly resistive material protects against pin holes, and other potential defects, and the like. Of course, there can be other variations, modifications, and alternatives.

Although the above has been illustrated according to specific embodiments, there can be other modifications, alternatives, and variations. Embodiments of the present invention can be applied in a method for forming high efficiency photovoltaic cells described in U.S. patent application Ser. No. 12/475,858 filed by inventor Howard W. H. Lee on Jun. 1, 2009 and be applied in a method and structure for forming thin film tandem photovoltaic cell described in U.S. patent application Ser. No. 12/562,086 filed by inventor Howard W. H. Lee on Sep. 17, 2009, commonly assigned and incorporated by reference herein for all purposes. Additionally, although the above has been described in terms of copper indium disulfide, other like materials such as copper indium gallium disulfide, copper indium aluminum disulfide, combinations thereof, and others can be used. Other materials may include CuGaS₂, CuInSe₂ (CIS), Cu(InGa)Se₂ (CIGS), Cu(InAl)Se₂, Cu(In,Ga)SSe, combinations of these, and the like. It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. 

1. A method for forming a thin film photovoltaic device, the method comprising: providing a transparent substrate comprising a surface region; forming a first electrode layer overlying the surface region; forming a copper layer overlying the first electrode layer; forming an indium layer overlying the copper layer to form a multi-layered structure; subjecting at least the multi-layered structure to a thermal treatment process in an environment containing a sulfur bearing species; forming a bulk copper indium disulfide material from at least the treatment process of the multi-layered structure, the bulk copper indium disulfide material having a surface region characterized by a copper poor surface region comprising a copper to indium atomic ratio of less than about 0.95:1, the copper poor surface region having an n-type impurity characteristics, the bulk copper indium disulfide material excluding the copper poor surface region forming an absorber region and the copper poor surface region forming at least a portion of a window region; forming a high resistivity transparent material overlying the copper poor surface region having the n-type impurity characteristics, the high resistivity transparent layer comprising a semiconductor material having an intrinsic semiconductor characteristic; and forming a second electrode layer having p-type impurity characteristics overlying the high resistivity transparent layer.
 2. The method of claim 1 wherein the copper poor region having the n-type impurity characteristics provides for a window layer.
 3. The method of claim 1 wherein the high resistivity transparent layer is optional.
 4. The method of claim 1 wherein the first electrode layer comprises a metal material.
 5. The method of claim 1 wherein the first electrode layer comprises a transparent conductive oxide material.
 6. The method of claim 1 wherein the first electrode layer is a transparent conductive oxide selected from: aluminum doped zinc oxide, indium doped tin oxide (ITO), or fluorine doped tin oxide.
 7. The method of claim 1 wherein the bulk copper indium disulfide comprising a thickness of copper sulfide material, the thickness of copper sulfide material being selectively removed using a solution of potassium cyanide.
 8. The method of claim 1 wherein the thermal treatment process of the copper poor surface comprises a temperature ranging from about 100 Degrees Celsius to about 500 Degrees Celsius.
 9. The method of claim 1 wherein the forming of the copper layer is provided by a sputtering process or plating process.
 10. The method of claim 1 wherein the forming of the indium layer is provided by a sputtering process.
 11. The method of claim 1 wherein the forming of the indium layer is provided by a plating process.
 12. The method of claim 1 wherein the bulk copper indium disulfide comprises p-type impurity characteristic.
 13. The method of claim 1 further comprising introducing an indium species in the window layer to cause formation of an n⁺-type semiconductor characteristic.
 14. The method of claim 1 wherein the bulk copper indium disulfide is mixed with a copper indium aluminum disulfide or copper indium gallium disulfide.
 15. The method of claim 1 wherein the sulfide bearing species comprise hydrogen sulfide in fluid phase.
 16. The method of claim 1 wherein the second electrode layer is a transparent conductive oxide material.
 17. The method of claim 16 wherein the transparent conductive oxide material is selected from aluminum doped zinc oxide, indium doped tin oxide (ITO), or fluorine doped tin oxide.
 18. The method of claim 1 wherein the high resistivity transparent material is selected from intrinsic zinc oxide material or intrinsic tin oxide material.
 19. A thin film photovoltaic device, the thin film photovoltaic device comprises: a substrate comprising a surface region; a first electrode layer overlying the surface region; a bulk copper indium disulfide material, the bulk copper indium disulfide material having a surface region characterized by a copper poor surface region comprising a copper to indium atomic ratio of less than about 0.95:1, the copper poor surface region having an n-type impurity characteristics; a high resistivity transparent material overlying the copper poor surface region having the n-type impurity characteristics, the high resistivity transparent layer comprising a semiconductor material having an intrinsic semiconductor characteristic; and a second electrode layer comprising a zinc oxide material having p-type impurity characteristics overlying the high resistivity transparent layer.
 20. A thin film photovoltaic device, the thin film photovoltaic device comprises: a substrate comprising a surface region; a first electrode layer overlying the surface region; an absorber region comprising a bulk copper indium disulfide material; a window region comprising a surface region of the bulk copper indium disulfide material, the surface region being characterized by a copper poor surface region comprising a copper to indium atomic ratio of less than about 0.95:1, the copper poor surface region having n-type impurity characteristics; a high resistivity transparent material overlying the copper poor surface region having the n-type impurity characteristics, the high resistivity transparent layer comprising a semiconductor material having an intrinsic semiconductor characteristic; and a second electrode layer comprising a zinc oxide material having p-type impurity characteristics overlying the high resistivity transparent layer.
 21. The thin film photovoltaic device of claim 20 wherein the high resistivity transparent material comprises intrinsic zinc oxide material or intrinsic tin oxide material having a doping level between about 1×10¹¹ and about 1×10¹³ cm⁻³.
 22. The thin film photovoltaic device of claim 20 wherein the high resistivity transparent material comprises a thickness between about 100 nm and 1000 nm and a resistance between 1 ohm/square and 0.0001 ohm/square.
 23. The thin film photovoltaic device of claim 20 further comprises a window layer comprising an n-type cadmium sulfide material overlying the copper poor surface region.
 24. The thin film photovoltaic device of claim 22 wherein the high resistivity transparent material comprises an intrinsic cadmium sulfide material. 